Bimetallic organic compounds and compositions containing same



7 2,934,548 Patented Apr. 26, 1960 BIMETALLIC ORGANIC COMPOUNDS AND COMPOSITIONS CONTAINING SAME The product of this invention may be referred to generally as a' multiple' salt of tin and antimony and is produced through reactions in which both the tin and the antimony are attached to a nucleus consisting of an organic residue by replacement of two hydrogen atoms. Joseph Fath, Morristown, NJ., assignor, by meme The other valences of the tin and the antimony are taken signments, to Heyden Ne t Ch i l c ti up either by direct linkage to a carbon atom of an organic acorporation of Delaware residue or by replacementof hydrogen atoms of an i organic residue, as may be desired. No g gfi gg 1,954 Compounds embodying the present invention contain the general grouping:-

29 Claims. (Cl. 260-4295) This invention relates to novel bimetallic organic comf X is derived from the Compound pounds and compositigns upon which they render a bone which 111 turn 18 defined as a difunct-ional 11101661113 havficial stabilizing effect when contained therein. More 8 replaceable yq atoms. particularly, the compositions so ff t d are Polymeric Examples of difunctional compounds of the general resin eompositions f hi h polyvinyl h i and Poly. structure H-XH are the dibasic acids, diphenols, mervinyl hl containing resins f h largest single 20 capto ac1ds and hydroxy acids. Specific compounds inm cluded with-1n this group are:

The problems encountered in preventing the degradasebacic acid tion by heat of these polymers during processing and dur- Azealeic acid ing the life of the article of commerce derived therefrom Adipic acid with respect to discoloration as well as to deterioration phthalic acid by constant exposure to light have been approached in succinic acid ny y Malic acid The most common means of protecting these poly- Fumaricacid mers against the efiects of light and heat is to incorporate Dodecenyl succinic acid therein stabilizers in the form of metal soaps, such as octenyl Succinic acid cadmium laurate, barium laurate, lead stearate, etcaor octadecyl succinic acid organo-metallic type compositions, such as dibutyl tin Resorcinol dilau-rate. The metal soaps cannot be used in all vinyl Catechol chloride containing resins due to limitations of special Thioglycouc acid properties required- The cream-metallic compounds, Thiomalic acid monobutyl ester as illustrated by dibutyl tin dilaurate, have special applis lf i i acid monoctyl ester cation to those resin compositions as require great clarity Maleic acid thioethyl ester and stability to light. Moreover, the organo-metalhc tin compounds generally function more effectively than Compounds wmammgfihe group described above are metal soaps. The metal soaps are cheaper than the 40 of the general configummom organo-metallic compounds but, in order to obtain A R B through their use results which approach those obtainable through the use of organo tin compounds, at high level of the soap is required, which overcomes the cost Y advantage and also defeats the purpose because f the wherein A, Y and Z are selected from the group consistfact that the clarity of the film and other physical proper- 0f alkyloxy, Yloxy, f y yl Y Q Y, y ties are adversely afiected by inclusion of high amounts ihloacylate, alkylthlo, l'y and alkarylthio radicalsof such soaps. Specific examples of HA, HY and HZ from which For the reasons stated, the organo-tin compounds are (this group derived are z-ethylhexanol, P1161101, noflyl preferred in many instances because of their high degree P1161101, XY161101, z-efllylheXoic acid, 016R! acid, 1911110 of performance. However, they are expensive materials aoid, y *P OPY 'Y acid, l 'y mercaptan, and many attempts have been made to find equally good octylthioglycolate, dibutylthiomalate, cyclohexylbetathiostabilizers of lower cost. butyrate, thiophenol, thiocresol, etc. R is defined as be- I have conceived, as a result of prolonged experimenlonging to the group consisting of alkyl, aryl, aralkyl, and tation and research, a new product which fulfills these r'ealkenyl radicals. Specific examples of R are methyl, quirements. It has the advantages of the organo-tin comethyl butyl, dodecenyl, phenyl, xylyl groups. In certain pounds while being greatly superior in its protective efiect cases R and A, Y or Z may be used interchangeably. upon polymeric resin compositions in which it is incorpo V Compounds embodying the present invention are shown rated and materially reduces the cost of the stabilizing in the table below. They are advanced as illustrated component of such compositions. and not by way of limitation.

- TABLEI Com- Name pound I Mgggeemonothioglyeolle acid lsooetyl ester) mono (antimony dlz-ethyl hexoate) CH" 0 H I; I V n (SC: s): (04H.- H.-- O) Sb-OCOIE [CH:C-O n-B-OHrC-OCsHn r'lfhe compounds shown in the above table maybe employed in halogen containingpolymeric compositions, such as polyvinyl chloride, from which finished goods may be prepared by milling, extrusion, coating, molding and the like. I

In order to demonstrate the eificacy of the compounds of this invention as stabilizers, a number of tests were carried out incorporating my compounds in a number of vinyl resins. Polyvinyl chloride films were prepared by milling, and the milled sheets were heat tested. The following specific example is typical of the procedures employed. 1 I i From 0.1 to 3 parts of my multiple salt stabilizer were incorporated into a mixture consisting of 100 parts by weight; of'resin, 35-50partsby weight of plasticizer 'or a mixture of plasticizers. The mixture was thoroughly blended untiIJconsidered uniform and then milled for five minutes on a 2 roll difierential speed mill heated to 320-330? F. A sheet was then removed from the mill and permitted to cool. 1 x 1 inch squares were cut out of the sheet at sample locations, placed on a flat glass plate and kept in a mechanical convection oven at 350 F. Sample squares were removed at 15, 30,

45, 60 and 120 minute periods. They were rated visually according to vthe amount of discoloration they exhibited. For purposes of color comparison, which was considered a measure of stabilizing efficiency, the following color rating scale was adopted. A ratingof 1 denoted no color, 3' denoted slight yellowing, 5 denoted yellowing, 7 denoted amber and 9 denoted black. Intermediate numbersdenoted colors of intermediate shades.

A summary of the performance of some of the compounds of Table I and the compositions in which they were used is given in Table II.

' TABLE n EXAMPLE I I, lnto a two IiterS-neck flask equipped with agitator,- thermometer, reflux condenser and Dean Stark tube were I C 7 Color Rating After- Oorn and N Resin 1 Plastlcizer I v 15 30 60 120 I.'1pai-t. Geon 10% EP (Goodrich), DioctylPhthalate,50parts.... 1 1 1 2 a 100 par s. II. 1.5 parts; VYNW (Bakelite), IOOparts. Dioetyl Phthalate, 45 parts, 1 1 1 1.5 2

g-62 5 parts (Rohm & aas V. 2parts--- Marvinol V-R-20 (Naugu- Dioctyl Phthalate, 25 parts, 1 1 1 1.5 2

tuck), 100 parts. Dioctyl sebacate, 25 parts. VIII. 1part.. Geon 101 EP, 100 parts.'. Dioctyl Phthalate, 22 parts, 1 1 2 2 3 l V G-62, 5 parts, Tricresyl Phosphate, 8 parts, 4G0 (Catrbon and Carbide), 8 x

pars. None..'..-.'..- Geon 101 EP, 100 parts Dioetyl Phthalate, parts.... 9 9 9 9 9 '1 Resin-Clean 101 EB, VYNW, Marvinol VR-ZO, are modified polyvinyl chloride resin powders manufactured by the above mentioned companies.

- i Plasticizer-G-62 is an epoxidized polymeric plasticizer manufactured by Rohin & Haas; 4G0 is tetraethylene glycol dl -2-ethylhexoate manufactured by Carbide and Carbon.

I The milled sheets produced by the incorporation of my compounds are not only extremely resistant to discoloraties to polyvinyl chloride resin compositions, thus making them valuable adjuncts to the vinyl processor.

My multiple salts may be prepared by various methods "of'which the two following are illustrative. These methods; using the same symbols as have heretofore been designated, may be represented by the following series of introduced 204 grams 2-ethylhexyl thioglycolate (1 mol),. grams -2 -ethylhexoic acid (1 mol), 202 grams sebacic' acid (1 mol), 161 grams of antimony oxide (0.55mol Sb O and.50 cc. xylene. The slurry was heated and agitated .at 180 C.200 C. under continuous reflux. When'27 cc. waterhad been collected and no further amount of water was eliminated, the reaction was discontinued and the mixture filtered from a small amount of unreacted antimony oxide.

Into another 2 liter 3 neck flask-equipped with stirrer, thermometer and reflux condenser were charged 252 grainsdibuty l tin oxide and 280grams oleic acid. "The mixture was heated to C. and the temperature was maintained for /2 hour. Thereupon the filtrate from the first part of this reaction was added and azeotropierefluxing was b egun until an additional 18 cc. of water had been collected. Upon completion of the reaction, execs! 7 xylene was removed by stripping. The residue consisted of mono(dibuty1 tin mono-oleate) mono (antimony nono Z-ethyl hexoate mono 2-ethylhexy1 thioglycolate) sebacate.

EXAMPLE II Into a two liter 3-neck flask equipped with agitator, thermometer, reflux condenser and Dean-Stark tube were introduced 400 grams lauric acid, 262 grams dibutyl thiomalate, 100 cc. xylene and 161 grams ofantimony oxide. The mixture was heated to 180 C.280 C. with agitation and refluxed at this temperature. Upon the elimination of 27 cc. water, the reaction was discontinued and the mixture filtered to produce a clear solution.

In a 1500 cc. beaker were placed 278 grams of dodecenyl succinic anhydride and 252 grams dibutyl tin oxide. The mixture was heated on a hot plate, with agitation, to 150 C. and maintained there for one hour. Following this, it was added to the clear filtrate prepared above and the mixture was placed in a 2 liter 3-neck flask equipped with agitator and distilling condenser. Xylene was removed from the solution under vacuum. The residue consisted of mono (dibutyl tin monodibutyl thiomalate) mono (antimony dilaurate) dodecenyl succinate.

It will be noted that in carrying out either of the foregoing methods, certain intermediates are produced. It is of course advantageous to separate the pure compound from the intermediates for use as a stabilizer. However, there is a considerable advantage chemically if such a purification procedure can be eliminated and I have found that when minor amounts of the intermediates are present together with the multiple salt, the performance and effectiveness of the multiple salt remains apparently unchanged. This may be due to a certain synergistic action which these intermediates evince when present with the multiple salts of this invention. Experience has shown, however, that these intermediates, when employed individually as stabilizers in vinyl halogen containing resins, show stabilizing activity only to a minor extent when present in amounts in which they are used to formcompounds of the present invention. a

The novel compounds of this invention have been hereinbefore described in connection with their primarily intended use in halogen containing vinyl polymers. They may moreover be used as stabilizers for other chlorinated materials, rubber anti-oxidants, lube oil additive and the like.

In the course of my research which resulted in the production of the multiple salts of this invention, numerous tests were carried out to determine the effectiveness of a simple mixture of a conventional organo tin stabilizer and an antimony salt. I have found that such a mixture had some stabilizing effect in some polymer compounds, but this effect was in nowise comparable to the remarkable results obtained by the multiple salts of this invention.

However, I consider such a mixture as a much less efii' wherein X isselected from the group consisting of hydrocarbo dibasic carboxylic acids, phenols, and mercapto acids, wherein antimony and tin are each linked to X by replacement of a single hydrogen atom, wherein R is selected from the group consisting of alkyl, aryl, and alliaryl radicals, and A, Y and Z are selected from the group consisting of alkoxy, aryloxy, alkaryloxy, acyloxy,

alkylthioacylate, alkylthio, arylthio and alkarylthio groups.

2. A compound according to claim 1, wherein X is the dodecenyl succinic acid radical.

3. A compound according to claim 1, wherein X is the octenyl succinic acid radical. 1

4. A compound according to claim 1, wherein X is the sebacic acid radical.

5. A compound according to claim 1, wherein X is. the catechoxy radical.

6. A compound according to claim 1, wherein X is the thiomalic acid m-onobutyl ester radical.

,7. A compound according to claim 1, wherein R comprises a butyl group.

8. A compound according to claim 1, wherein R comprises a xylyl group.

9. A compound according to claim 1, wherein R oomprises an ethyl group. p 3

' 10. A compound according to claim 1, wherein R comprises a phenyl group.

11. A compound according to claim 1, wherein R comprises a methyl group.

12. A compound according to claim 1, wherein A is the Z-ethylhexoic acid radical. p

13. A compound according to claim 1, wherein A is the thioglycolic acid isooctyl ester radical.

14. A compound according to claim 1, wherein A is the thiocresoxy radical.

15. A compound according to claim 1, wherein A is the laurylmercaptyl radical.

16. A compound according to claim 1, wherein A is the nonylphenoxy radical.

17. A compound according to claim 1, wherein Y is, the oleic acid radical.

18. A compound according to claim 1, wherein Y is the thiophenoxy radical.

19. A compound according to claim 1, wherein Y is the thioglycolic acid hexylester radical.

20. A compound according to claim 1, wherein Y is the phenoxy radical.

21. A compound according to claim 1, wherein Y is the 2-butyloctanoxy radical.

22. A compound according to claim 1, wherein Z is the thioglycolic acid isooctyl ester radical.

23; A compound according to claim 1, wherein Z is the thiomalic acid dibutyl ester radical.

24. A compound according to claim 1, wherein Z is the monolauryl mercaptyl radical.

25. A compound according to claim 1, wherein Z is the xylenoxy radical.

26. A compound according to claim 1, wherein Z is the lauric acid radical.

27. A compound according to claim 1, where X is the dodecenyl succinic acid radical, R is a butyl group, A

.is the 2-ethylhexoic acid radical, Y is the 2-ethylhexoic acid radical, and Z is the thioglycolic acid isooctyl ester radical.

28. A compound according to claim 1, wherein X is the dodecenyl succinic acid radical, R is a butyl group, A is the Z-ethylhexoic acid radical, Y is the xylenoxy radical, and Z is the thiomalic acid dibutyl ester radical.

29. A compound according to claim 1, wherein A, Y and Z are each thiomalic acid tridecyl ester radicals.

References Cited in the file of this patent UNITED STATES PATENTS 2,066,742 Schmidt "Jan. 5, 1937 2,226,530 Brown et al. Dec. 31, 1940 2,461,531 Cox et al. Feb. 15, 1949 2,556,420 Fincke June 12, 1951 2,581,931 Albert Jan. 8, 1952 2,641,588 Leistner et a1. June 9, 1953 2,680,726 Weinberg Iune8, 1954 2,826,597 Gloskey Mar. 11, 1958 

1. A COMPOUND OF THE GENERAL FORMULA 